Azo compounds from alkyl alpha-anilinotoluates

ABSTRACT

AZO COMPOUNDS CONTAINING A PHENYL, THIAZOLYL, BENZOTHIAZOLYL, THIADIAZOLYL OR THIENYL DIZAO COMPOUNENT AND AN N-ALKOXYCARBONYLBENZYL-N-ARALKYLANILINE COUPLING COMPONENET ARE USEFUL AS DYES FOR HYDROPHOBIC TEXTIEL MATERIALS SUCH AS POLYESTER FIBERS ON WHICH THE COMPOUNDS EXHIBIT IMPROVED BUILD-UP, EXCELLENT BRIGHTNESS AND SUPERIOR FASTNESS PROPERTIES SUCH AS FASTNESS TO LIGHT AND RESISTANCE TO SUBLIMATION.

3,660,374 AZO COMPOUNDS FROM ALKYL a-ANILINOTOLUATES Max A. Weaver, Herman S. Pridgen, and Clarence A.

Coates, Jr., Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, NY. N Drawing. Filed Nov. 5, 1968, Ser. No. 773,656

Int. Cl. C09]: 29/08, 29/24; D06p 3/52 US. Cl. 260-207 8 Claims ABSTRACT OF THE DISCLOSURE This invention relates to certain monoazo compounds and to polyester textile materials dyed with the novel monoazo compounds.

The novel monoazo compounds of the invention have the general formula R-N =l l -R --ll boa wherein R is a phenyl radical, a 2-thiazolyl radical, a 2-benzothiazolyl radical, a Z-thiadiazolyl radical, or a 2-thienyl radical;

R is p-phenylene; p-phenylene substituted with lower alkyl, lower alkoxy, halogen, or the group --NHA in which A is an acyl group; 1,4-naphthylene; or 1,4- naphthylene substituted with lower alkyl, lower alkoxy, halogen; or hydroxy;

R is alkylene of from 1 to about 2 carbon atoms;

R is hydrogen, lower alkyl, lower alkoxy, halogen, hydroxy, or lower alkoxycarbonyl; and

R is lower alkyl.

When applied to polyester textile materials according to conventional dyeing procedures, the compounds of the invention exhibit improved build-up, excellent brightness, and superior fastness properties, such as fastness to light and resistance to sublimation. The novel azo compounds impart various shades, ranging from yellow to blue, to polyester fibers. The improved fastness properties possessed by the novel azo compounds allows them to be employed in the dyeing of cotton-polyester fabrics receiving durable press processing. The superior sublimation fastness possessed by the compounds of the invention renders them particularly useful in the thermal fixation technique of dyeing polyester materials.

The diazo component represented by R can be unsubstituted, or, preferably, substituted with, for example, lower alkyl, lower alkoxy, aryl, nitro, halogen, lower alkylthio, lower alkoxycarbonylalkylthio, cyclohexylthio, arylthio, lower aralkylthio, formyl, lower allianoyl, lower alkoxycarbonyl, aroyl, lower alkanoylarnino, aroylamino, cyano, lower alkylsulfonyl, arylsulfonyl, lower alkylsulfonamido, trifluoromethyl, sulfamoyl, lower alkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, thiocyanato, etc. The alkanoyl groups can be substituted with substituents nitcd States Patent 0 ice such as halogen, phenyl, cyano, lower alkoxy, lower alkylthio, lower alkylsulfonyl, etc. The alkylsulfonyl groups can also be substituted, for example, with cyano, hydroxy, halogen and the like. The alkoxycarbonyl groups can be substituted, for example, with hydroxy or cyano. As used herein to describe a group containing an alkyl moiety, lower designates a carbon content from 1 to about 4 carbon atoms. Examples of the alkyl and alkoxy groups which can be present on the diazo components include methyl, ethyl, isopropyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, etc. Chlorine and bromine are typical halogen atoms. Methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Z-cyanoethylsulfonyl, 2- hydroxyethylsulfonyl, acetyl, propionyl, butyryl, isobutyryl, 3-chloropropionyl, cyanoacetyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 2 cyanoethoxycarbonyl, 2-hydroxyethoxycarbonyl, etc. are examples of the alkylsulfonyl, alkanoyl, and alkoxycarbonyl groups which can be present on the groups represented by R.

Acetamido, propionamido, methylsulfonamido, ethylsulfonamido, and butylsulfonamido are typical alkanoylamino and alkylsulfonamido substituents which can be present on the diazo component. Dimethylsulfamoyl, ethylsulfamoyl, butylsulfamoyl, diethylcarbamoyl, propylcarbamoyl, dibutycarbamoyl are examples of the alkylsulfamoyl and alkylcarbamoyl groups. The aryl groups which can be present on the diazo component including the aryl moiety of the arylthio, aralkylthio, aroyl and arylsulfonyl groups are preferably monocyclic, carbocyclic aryl such as phenyl and phenyl substituted, for example, with lower alkyl, e.g. tolyl; lower alkoxy, e.g. anisyl; halogen, e.g. chlorophenyl, bromophenyl; etc. Benzoyl, p-toloyl, p-chlorobenzoyl, p-nitrobenzoyl, pethoxyphenylthio, p-chlorobenzylthio, benzamido, p-toluoylamino, p-tolylsulfonyl, p-ethoxyphenylsulfonyl, etc. are examples of the aryl-containing groups which can be present on the groups represented by R. The acyl groups set forth below in the definition of A are further exam ples of the groups which can be present on the diazo component.

Illustrative of the phenyl groups which R can represent are 2-chloro-4-nitrophenyl, 4-nitrophenyl, 2-chloro-4-methylsulfonyl,

2,4-di (methylsulfonyl) phenyl, Z-methylsulfonyl-4-nitrophenyl, 2-nitro-4-methylsulfonylphenyl, 2-acetyl-4-nitrophenyl, 2-ethoxycarbonyl-4-nitrophenyl, 2,4-dinitro-6-chlorophenyl, Z-cyano-4,6-dinitrophenyl, 4-methoxycarbonylphenyl, 2-ethylsulfonyl-4,6-dinitrophenyl, 2-formyl-4,6-dinitrophenyl, 2,4-dinitro-fi-propionylphenyl, 2-ethoxycarbonyl-4,6-dinitrophenyl, 2-trifluoromethyl-4-nitrophenyl, 2,4-dicyanophenyl, Z-bromo-6-cyano-4-nitrophenyl, 4-nitro-2-sulfamoylphenyl, 2-nitro-4- dimethyl sulfamoylphenyl, 4-cyanophenyl, 4-methylsulfonylphenyl, 4-trifluoromethylphenyl, 4-chlorophenyl, 4-ethylsulfamoylphenyl, 4-acetylphenyl, 4-ethylcarbamoylphenyl, 2-carbamoyl-4-nitrophenyl,

2-methylsulfonyl-4-thiocyanatophenyl, 2,6-dichloro-4-nitrophenyl, 2-nitro-4-thiocyanatophenyl, 2-chloro-6-cyano-4-nitrophenyl, 2-cyano-4-nitrophenyl, 2-chl0ro-4-cyanophenyl, 2-chloro-4-ethoxycarbonylphenyl,

and the like. Preferably, the substituted phenyl group R contains not more than three substituents at the para and ortho position.

Typical heterocyclic groups represented by R include 2-thiazolyl,

-nitro-2-thiazolyl,

5 -bromo-2-thiazolyl, 5-thiocyanato-Z-thiazolyl, 4-trifiuoromethyl-Z-thiazolyl, 4-ethoxycarbonyl-2-thiazolyl,

5 -cyano-2-thiazolyl, S-acetamido-Z-thiazolyl, 4-methylsulfonyl-2-thiazolyl, 4-methyl-S-nitro-Z-thiazolyl, 2-benzothiazolyl, 6-methylsulfonyl-Z-benzothiazolyl, 6-ethoxycarbonyl-2-benzothiazolyl, 6-cyano-2-benzothiazoly1, H 6-sulfamoyl-Z-benzothiazolyl, 6-thiocyanato-2-benzothiazolyl, 6-N,N-di-methylsulfamoyl-2-benzothiazolyl, 4,6-dichloro-2-benzothiazolyl, 4-methyl-6-nitro-2-benzothiazolyl,

S-methyl- 1,3 ,4-thiadiazol-2-yl,

S-thiocyanato-l ,3 ,4-thiadiazol-2-yl, S-cyclohexylthiol 3 ,4-thiadiazol-2-yl, S-ethylthio- 1,3 ,4-thiadiazol-2-yl,

5-phenylthio-1,3 ,4-thiadiazol-2-y1,

S-acetarnido- 1 ,3 ,4-thiadiazol-2-yl,

5-chloro-1,3 ,4-thiadiazol-2-yl, S-beta-cyanoethylthio-1,3,4-thiadiazol-2-yl, 5-ethoxycarbonylmethylthio-1,3,4-thiadiazol-2-yl, S-phenylsulfonyl-1,3,4-thiadiazol-2-yl, 3-methylsulfonyll ,2,4-thiadiazol-5-yl, S-butylthio-1,2,4-thiadiazol-5-yl, 5-benzoyl-3-nitro-2-thienyl, 3-nitro-S-p-toluoyl-Z-thienyl,

3 ,5 -di (methylsulfonyl -2-thienyl, 5-methylsulfonyl-3 -nitro-2-thienyl, 5-ethylsulfamoyl-3-nitro-2-thienyl,

S-ethoxycarb onyl-2-thienyl,

3 ,5-dinitro-2-thieny],

3 -nitro-2-thienyl, etc.

Preferred groups represented by R have the formula R is hydrogen, halogen, cyano or nitro;

R is nitro, lower alkylsulfonyl, thiocyanato or sulfamoyl;

R is hydrogen, halogen, forrnyl; lower alkanoyl, lower alkoxycarbonyl, trifiuoromethyl, lower alkylsulfonyl, cyano, sulfamoyl, or carbamoyl;

R is lower alkyl, lower alkoxy, nitro, halogen, lower alkylsulfonyl, carbamoyl, lower alkylcarbamoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl, cyano, thiocyanato, trifluoromethyl, phenyl or substituted phenyl;

R is lower alkyl, lower alkoxy, nitro, halogen, lower alkylsulfonyl, substituted lower alkylsulfonyl, car'barnoyl,

lower alkylcarbamoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl, cyano, thiocyanato, lower alkylthio, cyclohexylthio, phenylthio, substituted phenylthio, or trifiuoromethyl;

R is lower alkyl, lower alkoxy, halogen, lower alkylthio, benzylthio, cyclohexylthio, phenylthio, substituted phenylthio, phenyl, substituted phenyl, benzyl, lower alkylsulfonyl, lower alkanoylamino, lower alkylsulfonamido, benzamido, lower alkoxycarbonyl, lower alkoxycarbonylalkylthio, thioeyanato, sulfamoyl, or lower alkylsulfamoyl;

R is lower alkylthio, cyclohexylthio, benzylthio, or lower alkylsulfonyl; and

R is lower alkanovl. benzoyl, or substituted benzoyl.

Examples of the alkyl and alkoxy groups and halogen atoms which can be present on the phenylene and naphthylene groups represented by R are set forth above in the definition of the diazo groups. The acyl groups represented by A in the group NI-IA, which can be present on the phenylene ring represented by R, can be formyl, lower alkanoyl, aroyl, cyclohexylcarbonyl, lower alkoxycarbonyl, aryloxycarbonyl, lower alkylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbamoyl, arylcarbamoyl, furoyl, etc. The alkanoyl and alkylsulfonyl groups can be substituted as described above in the definition of R. Acetyl, propionyl, butyryl, cyanoacetyl, ehloroacetyl, phenylaeetyl, methoxyacetyl, methylthioacetyl, methylsulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2-eyanoethylsulfonyl, Z-methoxyethylsulfonyl and 2 chloroethylsulfonyl, are examples of the alkanoyl, alkoxycarbonyl, and alkylsulfonyl groups which A can represent. The aryl group of the aroyl, aryloxycarbonyl, arylsulfonyl, and arylcarbamoyl group is preferably monocyclic, carbocyclic aryl such as unsubstituted phenyl and phenyl substituted with, for example, lower alkyl, lower alkoxy, halogen, etc. Tolyl, anisyl, p-bromophenyl, and c,p-dichloro-phenyl are typical of such aryl groups. Dimethylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, and butylcarbamoyl are illustrative alkylcarbamoyl groups which A can represent.

Examples of the substituents represented by R and R appear hereinabove.

Particularly fast dyeings on polyester materials are obtained from the compounds having the formula on R 2 were? 9,

t HA CH2-COR wherein R represents a group having the formula 6 R U ill? at i t 11 IO a t 12 2 10 I or R R it li ks u wherein R is hydrogen, cyano, or nitro;

R is nitro, lower alkylsulfonyl, or thiocyanato;

R is hydrogen, halogen, formyl, lower alkanoyl, lower alkoxycarbonyl, trifiuoromethyl, lower alkylsulfonyl, or cyano;

R is cyano, nitro, lower alkylsulfonyl, or lower alkoxycarbonyl;

R is cyano, nitro, lower alkylsulfonyl, lower alkoxycarbonyl, or thiocyanato;

R is lower alkyl, lower alkylthio, cyclohexylthio, phenylthio, lower alkylsulfonyl, or lower alkoxycarbonyl;

R is lower alkylthio or lower alkylsulfonyl; and

R is lower alkanoyl, benzoyl, lower alkylbenzoyl, lower alkoxybenzoyl, halobenzoyl, or nitrobenzoyl;

A is lower alkanoyl, benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl, or lower alkylcarbamoyl;

R is hydrogen, lower alkyl, lower alkoxy, or halogen; and

R is lower alkyl.

The novel azo compounds of the invention are prepared according to known procedures by diazotizing an amine having the formula RNH and coupling the resulting diazonium salt with a compound having the formula 0 ore wherein R, .R R R and R are defined above. The diazotizable amines RNH are well-known compounds 75 C. and at 1500 p.s.i. until the hydrogen uptake ceases. Enough ethanol is added to the mixture from the autoclave to dissolve the product at C. After removal of the nickel catalyst by filtration, the filtrate is drowned in water. The product is collected by filtration and dried in air. The yield is 79.6 g. of methyl tit-(3- acetamidoanilino)-p-toluate which melts at 143-145 C. Methyl 0c (3 acetamidoanilino)-p-toluate (29.8 g.), benzyl chloride (25.2 g.) and N,N dimethylformamide (30 ml.) are heated and stirred at 95-100 C. for 1.5 hr., and then triethyl amine (28.0 ml.) is added dropwise. Heating is continued at 95l00 C. for an additional hour. The reaction mixture is drowned in 850 ml. of water plus 150 ml. of acetone. The crystalline product is collected by filtration and recrystallized from 1200 ml. of acetone. The product melts at 182-185 C. and has the structure:

Analysis.Calcd. for C H N O (percent): C, 74.0; H, 6.2; N, 7.2. Found (percent): C, 74.0; H, 6.0; N, 7.6.

The aniline compounds, substituted with the group NHA, employed in the synthesis of the couplers are prepared by nitrating an acylanilide and reducing the nitro compound to the corresponding acylamidoaniline. Alternatively, the benzyl substituents can be added to a nitroaniline, by the reactions described above, followed by reduction of the nitro group and acylation of the resulting amino group.

The following table discloses several couplers of Formula II which are prepared according to the procedures described above.

which can be prepared according to published procedures. The couplers of Formula II are prepared by known techniques. For example, an aniline compound can be reacted with an alkoxycarbonylbenzaldehyde to obtain the anil which is reduced to give the corresponding N-alkoxycarbonylbenzylaniline compound which can be further reacted with a benzyl halide or aralkyl halide, yielding the coupler. The N-alkoxycarbonylbenzylaniline compound can also be obtained by reacting an aniline with an alkoxycarbonylbenzyl halide. The reactions can be performed in various organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidinone. The N alkoxycarbonylbenzylaniline compounds also can be prepared by reacting a nitrobenzene compound with an alkoxycarbonylbenzaldehyde with simultaneous reduction. The synthesis of a typical coupler is illustrated by the following example.

A mixture of 3'-nitroacetanilide (72.0 g), 85 g. methyl terephthalaldehydate (85.0 g., 85% pure), ethanol (100 ml.), and Raney nickel (12.0 g.) is hydrogenated at The following examples will further illustrate the preparation of representative azo compounds of the invention.

EXAMPLE 1 To 5 ml. conc. H is added 0.72 g. of NaNO with stirring. This solution is cooled and 10 ml. 1:5 acid (1 part propionic acid:5 parts acetic acid) is added below 10 C. This is stirred and 1.72 g. 2-chloro-4-nitroaniline is added followed by 10 ml. additional 1:5 acid, all at 0-5 C. The diazotiazation is stirred at 05 C., for 3 hr. and then added to a chilled solution of 3.87 g. methyl 0!.- (S-acetamido N benzylanilino) p toluate dissolved in a mixture of 60 ml. 1:5 acid and 40 ml. 10% hydrochloric acid. The coupling is kept cold (below 5 C.) and buffered with solid ammonium acetate until neutral to Congro Red paper. After allowing to couple for 2 hr., the product is drowned in water, collected by filtration, washed with water and dried in air. The azo compound produces bright red dyeings having excellent fastness to light and sublimation on polyester fibers and has the Cl NHCOCHa EXAMPLE 2.

P-nitroaniline (6.9 g.) is dissolved in 5.4 ml. cone. H 50 and 12.6 ml. water. This solution is poured on 50 g. of crushed ice, and then a solution of 3.6 g. NaNO in 8 ml. water is added all at once. The diazotization is stirred at -5" C. for 1 hr., and then the solution is added to a chilled solution of methyl u-(3-acetamido-N-benzylani1ino)-p-toluate (22.5 g.) dissolved in 250 ml. of 1:5 acid. The coupling is kept at 05 C. and neutralized with ammonium acetate until it is netutral to Congo Red paper. After coupling 2 hr., the mixture is drowned in water. The product is collected by filtration, washed with water, and air dried. It has the following structure NHCOCHa This compound produces bright scarlet shades on polyester fibers.

EXAMPLE 3 Substitution of 2.05 g. of 2-chloro-4-methylsulfonylaniline in Example 1 for the amine diazotized in that example yields the dye 4-(2'-chloro-4-methylsulfonylphenylazo) 3 acetamido N benzyl-N-(4'-methoxycarbonylbenzyl) aniline which give orange dyeings, having outstanding resistance to sublimation, on polyester fibers.

EXAMPLE 4 2-cyano-4,6-dinitroaniline (2.07 g., .01 m.) is dissolved in 75 ml. of cone. H 80 at about 0 C. A nitrosyl sulfuric acid solution prepared by adding 0.72 g. NaNO to 5 ml. of cone. H 50 is added portionwise at -5 to 0 C. after being stirred 20 min. at about 0 C., the diazonium solution is added to a cold solution of methyl oz (3 acetamido N benzylanilino)-p-toluate (3.88 g., .01 m.) dissolved in 60 ml. of H SO plus 40 ml. of 1:5 acid. After allowing to stand 15 min. the coupling mixture is drowned with water. The product is collected by filtration, washed with water, and dried in air. The product WQ 1 GHQ-000cm CN NHCO CH producets bright reddish blue shades on polyester fibers.

EXAMPLE 5 2,6-dichloro-4-nitroaniline (2.07 g., .01 m.) is dissolved in 10 ml. of cone. H at room temperature. The solution is cooled to 0 C. and 0.72 g. of NaNO in 5 ml. of cone. H SO is added at 0 C. The reaction mixture is stirred at 05 C. for 2 hr. and is then added to a cold solution of methyl a-(N-benzylanilino) p-toluate (3.3 g.) dissolved in ml. of 1:5 acid. The reaction mixture is buffered by the addition of solid ammonium acetate until 21 test sample is neutral to Congo Red paper. After allowing to couple 1 hr., the mixture is drowned with water; the product is collected by filtration, washed with water, and dried in air. The product, which has the structure /CH COOCH:

A CH2- produces brownish yellow shades on polyester fabrics.

EXAMPLE 6 2-chloro-4,G-dinitroaniline (2.18 g.) is diazotized and coupled to Z-methoxy 5 acetamido-N-benzyl-N-4-methoxycarbonyl-benzyl) aniline according to the procedure described in Example 1. The product, 4-(2'-chloro-4',6'- dinitrophenylazo)-2-methoxy 5 acetamido-N-benzyl-N- (4-methoxycarbonylbenzyl)aniline, produces a Navy blue shade on polyester fibers.

The azo compounds set forth in Table II, are prepared according to the procedures described in Examples l-6 and conform to the general formula wherein n is 0, 1 or 2.

The color for each of the compounds appearing in Tables II through VI refers to dyeings on polyester fibers.

TAB LE II Position of CO0 R Color Yellow-brown:

Do. Red-brown.

Brown. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red. Red.

mmmmmmm NHCOCI-I;

bright fast red shades on polyester fibers and has the structure NHCOCH;

EXAMPLE 130 The thiazolylazo compounds appearing in the examples l of Table III are prepared by the procedures described To of 2'a,mm'6methylsulfonylbenzothlazole in Examples 97 and 98 and conform to the general Suspended 24 added H2504 After all the amine has dlssolved, the solutlon is cooled and a formula solution of 0.84 g. NaNO in 5.0 ml. conc. H 50 1s added R3 portionwise below 0 C. The diazotization is stirred for N o R I R Q 2 hr. at about 0 C. and then added to a solution of 3.26 g. methyl a-(3-acetamido-N-benzylanilino)-p-toluate diss solved in 75 ml. of 15% H 80 all below 15 C. The (1,) CH2 0 temperature is kept at 0-5 C. for 1 hr. and then the 1| coupling mixture is drowned with water. The product Com is collected by filtration, washed with water, and air TABLE III Position Example No. R5 (1') R9 B3 --COOR4 R4 Color S-NOz 3-CH3 CH2- H 4 CH; Blue.

5-NO2 3-NHCOCH3 CHzCHz H 4 CH3 D0. 5-NO2 3-NHCOCH3 CHz 4-0113 4 C2H5 D0. 5-NO2 B-NHCOCHZOCH; -CHz- 4-CH3 3 CH3 D0. 5-NOz 3-NHCHO CH2 3-COOCH3 3 3-COOCH3 Do. s-No 3-NHCOCH2CN -0H4- H 4 -CII3 Do. B-NOz 3-NHCOCHzCaH5 -CHz H 4 -O4He-n D0. 5-NO- a-NHcoceHs -CHz H 2 CH3 Do. 5-NOz 3-NHCONHC2H5 CHz H 4 -OH; Do. 5-NO2 3-NHCONHC5H5 CH2 H 4 C2H Do. 5-NO2 3-NHCOOC2H5 CH2 H 4 CH3 DO. fi-NOz 2-CH3-5-NHCOCH3 CHz H 4 --CH3 D0. 5-NO2 2-OOH3-5-NHCOCH3 -CH2- H 4 -CH3 Blue-green. 5-NOz 2-OCH3-5-NHCOC6H5 --OH2 H 3 C2H5 Do. 5-NO 3-NHCoOeH -GH2- H 4 CH3 Blue. 5-CONH2 3-NHCOOC2H5 CH4CHz H 4 C3H n Red. CN B-NI-ICOCH H4- H 4 -CH3 Violet. 6-CN 3-NHCOCH; -CH2 4-COOCH; 4 --CH3 Do. 5-SO2CH3 3-NHCOOH3 CH2 H 4 OH; Do. 5-SOZCH3 3-NHSOzCH3 CH2- H 4 CH3 Do. 5-Br 3-NHCOCH3 CH: H 4 CH3 Red. 5-01 S-NHSOzCBHg-P-Cl CH2- H 4 -CH3 Do. 5-COOCHH5 3-NI'ICOCH3 CHz- H 4 -CH3 Do. 4 C4H5 3-NHCOCH3 CH' H 4 GH; Do. 4-01 3 3-NHCOCH3 -CH2- H 4 C1I3 D0. 4-CH3-5-SCN 3NHCOCH3 -OH2 H 4 -CH3 D0. 4-NHCOCH3 3-NHCOC He-n CH2 H 4 CHQ Do. 4-CH3-5-NO2 3-NHCOOI-I2OCeH5 CH2- H 4 CH3 B1110- 4-CH3-5-NO2 3-NHSOzCHa CH2 H 4 -0H@ Do. 4-CH4-5-NO1 3-NHSO2C0H5 -CHz H 4 CH3 D0.

EXAMPLE 129 dried. The azo compound obtained gives fast red dyeings on polyester fibers and has the structure: Sod1um nitrite (0.76 g.) IS added portionwlse to 5 ml. of cone. H250 This solution is cooled in an ice bath and P 10 ml. 1:5 acid is added, keeping the temperature below Q Z- )-N=N -l\l 15 C. This mixture is stirred at 0-5 C. and 1.75 g.

Nlicoclr CH2 COOCHS of Z-ammo-6-cyanobenzoth1azole is added, followed by 10 ml. of 1:5 acid. The diazotization is stirred at 0 5 c. 3 3 m??? Tablle IV are prepared y the o for 2 hr. and is then added to a solution of 3.26 g. methyl i 1 zig fi z es 129 and 130 and Con a-(3-acetamido-N-benzylanilino)-p-toluate in 100 ml. of R3 1:5 acid. The coupling is buffered with solid ammonium s 1 acetate and allowed to react at about 5 C. for 2 hr. After (30 |i S drowning in water, the product is collected by filtration, washed with water, and dried in air. The product produces i l 2 8 TABLE IV Positionof Example No. R (Y)n R2 R3 COOR4 R4 Color H CH2 H 4 CH3 Red. 8-CH --OHz H 4 CH; Red. 3-Cl -CH2 H 4 OH; Red. Z-CH; CH2 H 4 CH Red. 3-NHCOOH 0H4GHe H 4 CH3 Red. 2-OCH3-3-NHCOCH3 -CH2 H 4 CH3 Violet 3-NHCOC01I5 CII4 H 4 -CH; Red. 3-NHSO2CH3 -CH2 4-C1Is 3 -C2H Red. 3-NHSO2CH3 -CH1 H 2 -CH3 Red. 3-NHC0NHG4H5 -CH2 H 4 CH Red. 3-NHCOCH3 CH2- H 4 CHa Red.

TABLE IV-Continued Position of Example No. R (Y) n R R C O R R Color 142 6-NO2 H -CHz- H 4 CH3 Bordeaux. 143 G-NOz SCI'II) CH2- H 4 CH D0. 144-... fi-NOz 3-NHCOCH3 CH2 4-CH3 4 CH3 Violet. 145.-.. fi-NOz 2-CHy5-NHCOCH3 -CH2 4-CH3 4 CH Do. 146--. 6-NOz 2-OCHa-NHCOCzH CHz 4-CH; 4 CH3 Blue. 147 4,6-di-NO2 3-NHCOCHa CH2 H 4 -CH3 Do. 148.- 4-Br-6-SO2CH 3-NHCO CH CHz- H 4 CH3 Violet. 149-. 4-Cl 3-NHCOCH3 -CH2- H 4 CH3 Red. 150-- 4.6-di-Cl 3-NHCOCH -CHz H 4 CH3 Red. 151-- 6-Br S-NHCOCHa --CH2 H 4 --CH3 Red. 152.... (i-SOzNHz 3-NHCOCH3 --CHz H 4 CH Red. 153.- G-S OzN (CHrQz 3-NHCO CH3 -CH2 H 4 CH3 Red. 154-- fi-CO OCzHa 3-NHCO CH3 CH2- H 4 CH3 Red. 155-- G-COCHa 3-NHCOCH3 CH2- H 4 CH3 Red. 156.- G-NHCOCH; 3-NHCOCH3 -CH2 H 4 -CH3 Red. 157-- 6-5 CH 3-NHCO CH3 -CHz H 4 -CH Red. 158-- 6-SCH 3-NHCOCH CHz H 4 -CH Red. 159.- G-CsHs 3-NHCO CH3 --CH2- H 4 -CH3 Red. 160 G-SOzCHzCHzCN 3-NHOOCH3 CH2'- H 4 -CH3 Pink.

EXAMPLE 161 tron of methyl a- 3-aceta1mdo-N-benzylaml1no) p-tolu- Sodium nitrite (0.72 g.) is added to 5 ml. of conc. H 80 with stirring. The solution is cooled and ml. of 1:5 acid is added below C. The mixture is cooled further and 2-amino-5-ethylthio-1,3,4-thiadiazole (1.61 g.) is added at 05 C., followed by an additional 10 ml. of 1:5 acid. After stirring at 0-5 C. for 2 hr the diazonnium solution is added to a cooled solution of methyl or- (3-acetamido-N-benzylanilino)p-toluate (3.87 g.) in 60 ml. of 1:5 acid, plus 40 ml. of 10% HCl. The reaction mixture is buifered with ammonium acetate until a test sample is neutral to Congo Red paper. The coupling mixture is allowed to stand for 1 hr. and then water is added to precipitate the dye. The product is collected by filtration, washed with water, and dried in air. The product, which has the structure CH ccoca NHCOCHB 2 G produces brilliant scarlet shades on polyester fiber and possesses excellent fastness properties.

EXAMPLE 162.

To 1.63 g. Z-amino-S-methylsulfonyl-1,3,4-thiadiazole slurried in 24 ml. water, is added 14' ml. conc. H 80 The resulting solution is cooled to 0 C. and a solution of 1.44 g. NaNO in 10 ml. conc. H 804 is added below 5 C- The diazotization is stirred at ice-bath temperature for 2 hr. It is then added to a cold solution of 4.4 g. 3-benzamido-N,N-di(3 methoxycarbonylbenzyl)aniline in 100 ml. of 1:5 acid. The coupling is buffered with solid ammonium acetate and allowed to stand 2 hr. It is then drowned in water. The dye is collected by filtration, Washed with water, and air dried. The azo compound obtained dyes polyester fibers bright red shades having excellent fastness properties and has the formula OOCH3 N. o CO- COOCHQ EXAMPLE 163 Sodium nitrite (0.72 g.) is added to 5 m1. conc. H 80 The solution is cooled and 10 ml. of 1:5 acid is added below 15 C. After cooling further, 5-amino-3-methylthio-l,2,4-thiadiazole is added below 5 0., followed by an additional 10 ml. of 1:5 acid at the same temperature. The diazotization reaction is stirred at 05 C. for 2 hr., and then the diazonium solution is added to a cold soluate (3.87 g., .01 In.) dissolved in 60 m1. of 1:5 acid, plus 40 ml. of 10% HCl. The coupling is kept cold and is buffered by the addition of ammonium acetate until a test sample is neutral to Congo Red paper. The coupling is allowed to stand 1 hr. and is then drowned with water. The product is collected by filtration, washed with water and dried in air. The dye -COOCH NHCOCH produces beautiful red shades on polyester fibers and has excellent lightfastness and resistance to sublimation.

The thiadiazolylazo compounds set forth in the examples of Table V are prepared by the procedures described in Examples 116 through 163 by diaziotizing the appropriate 2-aminothiadiazole and coupling the resulting diazonium salt with an alkyl u-N-benzylanilinotoluate. The compounds of Table V conform to the general formula R-lFN- -N Q \CH2--COOCH3 in which diazo component R is a group having the structure 1 1'. N R L j- (1 3 or 15 D- (1 2 i) s .v s a a I TABLE V Example N 0. R, R diazo isomer (Y) 11 Color CH S-1,3,4 H Oran e Cities-1,3,4 3-CH3 Do. OH3S'1,3,4 3-NHC 002115 Scarlet. CH3S-1,3,4 B-NHCO CaHs Do. CzHrS-1,3,4 3-NHCONH2 D0. n'C Hos-l 3,4 3-NHCOCH Do. nC4 oS-1,3,4 3-NHSQ2CH3 0- CeHuS-l,3,4 3-NHCOCH Do. OH SO2-1,3,4 a-Nnooooim Violet CH SO21,3,4 3-NHCOC6H5 Do. CBH5'1,3,4 3-NHC 0 CH Orange CH3-1,3 4 3-NHSO2CH3 D0. oi-0611.4 3-NHCO on. Red. p-CH3-CoH4-l,3,4 3-NHCOCH Red. p-OH3O-OeH4-1,3,4 S-NHC OCH Red. (ll-1,3,4 s-NHoooH. Red. 3-NHCOCH Red. 3-NHC 0 CH3 Red. 3-NHCOOC2H5 Red. 3-NHSO C2H5 Red. 3-NHCONHC2H4 Red. 3-NHCOC2H5 Red. 3-NHCOCH3 Violet. 2-0 CHa-5-NHCOCH D0. z-oni-a-Nnooona Do. 189 CaH5CH2S1,2,4 3-NHCOCH; Red. 190 (OH3)2OIIOH2S-1,2,4 3-NHCOCH Red.

1 5 EXAMPLE 191 To 5 ml. of concentrated sulfuric acid is added portionwise 0.72 g. of sodium nitrite with stirring. The nitrosyl sulfuric acid solution is cooled and 10 ml. of 1:5 acid (1 part propionic to 5 parts acetic) is added below 10 C. 2-amino-3-nitro-5-isobutyrylthiophene is added to acid solution followed by 10 ml. of 1:5 acid, all of -5 C. The mixture is stirred at 0-5" C. for one hour. The diazonium solution is added to a cold solution of methyl 16 polyester textile materials by the heat fixation technique described in US. Pat. 2,663,612 and in the American Dyestuff Reporter, 42, 1 (1953). The following procedure describes how the azo compounds of the invention can be applied to polyester materials by the heat fixation technique.

EXAMPLE 211 A mixture of: 500 mg. of the compound of Example 4, 150 mg. of a a-(S-acetamido-N-benzylanilino)p-toluate (3.87 g.) in 60 10 sodium lignosulfonate dispersing agent (Marasperse N), 0f P1115 0 of HCl. The 00 P g 150 mg. of a partially desulfonated sodium lignosulfonate mixture is stlrred occaslonally for 1 hr. and is then (Marasperse CB), 0.5 ml. glycerin, and 1.0 ml. of drowned with water. The blue dyeus collected by filt awater is ground in a microsize container (an accestion, washed with water, and dried in arr. The dye. 15 ry for a 1 quart size Szegvari Attritor) for approximately 3.5 hours. Enough Az-inch stainless steel 8 l' N/ balls are added to provide maximum grinding. When the (CHQZCH S grinding is complete, the entire contents are poured into COOCF a beaker and 100 ml. of water are used to wash the re- NHCOCHS maining dye paste from the micro-container. The dye paste 1s then heated slowly to 65 C. with continuous imparts fast blue shades to polyester fibers. mixing The azo compounds of Table VI are prepared by the A thickener and penetrating mixture is prepared by procedure described in Example 191 by substituting the mixing. appropriate aminothiophene and coupling components. 1 ml. of a complex diaryl sulfonate surfactant (com- The compounds conform to the formula pound 8-S),

e 3 ml. of a 3% solution of a sodium N-methyl-N-oleoyltaurate (Igepon T-Sl), 1m 8 ml. of a 25% solution of natural gums (Superclear s 3O SON), and sufficient water to bring the volume to 100 3 --CooCH3 ml. The thickener and penetrating mixture is added to (Y) the dye paste, the volume is adjusted to 200 ml. and the TABLE VI Example No. R (Y) n R3 Color 3-NOHOCH3 H Blue. 3-NHCOC5H5 H D0. 3-NHOOOZH5 4-011 Do. B-NHSOzCH; H Do. 3-NHCOCH3, 4-Br Do. 3-NHCHO H D0. 3-NHOOCaH11 H DO. 3'NHCOC6H5 H Do. 3-NHCONHC2H5 H Do. 01 2-0 CH3-5-NHC 0 CH3 I-I Blue-green. 202... 5-(CHs)zCHCO-3-N0z 3-NHCOC2H Cl H e. 203 B-D-NOZ'CGH4CO3-NO2 3-NHOOOH3 H Do. 204 5-p-Cl-CsH4CO-3-N02 3-NHCOCH3 H Do. 205 s-onaonzoHra-Noz 3'NHSO2C2H4CI H Do. 206.-. 3,5-di-NO2 3-NHCOCH3 H Blue-green. 207.-- -di-SOzCH3 3-NHCOCH(CH3)1 H Turquoise. 208.. -N02 3-NHCOC4HTI1 H Blue. 209 5-COOCzH5 3-NHCOCH3 H Do.

The compounds of the invention can be used for dyeing linear polyester textile materials in the manner de- The azo compound (0.1 g.) is dissolved in 10 cc. of 2- methoxyethanol. A small amount (35 cc.) of a 3% sodium lignin sulfonate aqueous solution is added, with stirring, and then the volume of the bath is brought to 300 cc. with Water. Three cc. of an anionic solvent carrier (Tanavol) is added to the bath and 10 grams of a textile fabric made of poly(ethylene terephthalate) fibers is placed in the bath and worked 10 minutes without heat. The dyeing is carried out at the boil for one hour. The dyed fabric is removed from the dyebath and scoured for 20 minutes at 80 C. in a solution containing 1 g./l. neutral soap and l g./l. sodium carbonate. The fabric is then rinsed, dried in an oven at 250 F. and heat set (for the removal of residual carrier) for 5 minutes at 350 C.

The compounds of the invention can also be applied to mixture is agitated for 15 minutes. The dye mixture is then filtered through folded cheesecloth to remove the stainless steel balls and it then is added to the reservoir of a Butterworth padder where it is heated to about -60 C.

10 g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of a fabric of 65 35 spun poly(ethylene terephthalate) /cotton fibers are sewn together, end-to-end, and padded for 5 minutes of continuous cycling through the dye mixture and between three rubber squeeze rollers of the padder. Dye mixture pick-up is about based on the weight of the fabrics.

The padded fabrics are then dried at 200 F. and then heat-fixed for 2 minutes at 415 F. in a forced air oven. The dyed fabrics are scoured for 20 minutes at -70 C. in a solution containing 0.2% sodium hydrosulfite, 0.2% sodium carbonate and 1.7% of a 3% solution of sodium N-methyl-N-oleoyltaurate and then dried. The dyed fabrics possess excellent brightness and exhibit outstanding fastness to light and sublimation when tested according to the procedures described in the 1966 edition of the Technical Manual of the American Association of Textile Chemists and Colorists.

The heat fixation dyeing procedure described above can be varied by the substitution of other dispersing agents, surfactants, suspending agents, thickeners, etc. The tem- 17 perature and time of the heat-fixation step can also be varied.

Polymeric linear polyester materials of the terephthalate sold under the trademarks Kodel, Dacron and Terylene are illustrative of the linear aromatic polyester textile materials that can be dyed with the compounds of our invention. Examples of linear polyester textile materials that can be dyed with the compounds of the invention are those prepared from ethylene glycol and dimethylterephthalate or from cyclohexanedimethanol and dimethylterephthalate. Polyesters prepared from cyclohexanedimethanol and dimethylterephthalate are more particularly described in US Pat. 2,901,446. Poly(ethylene terephthalate) polyester fibers are described, for example, in US. Pat. 2,465,319. The polymeric linear polyester materials disclosed in US. Pats. 2,945,010, 2,957,745, and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C. The poly(ethylene terephthalate) fibers which are dyed with the compounds of the invention are manufactured from a melt of a polymer having an inherent viscosity of at least 0.35 and preferably, about 0.6. The inherent viscosity of the poly(1,4-cyclohexylenedimethylene terephthalate) polymer is also at least 0.35. These inherent viscosities are measured at 25 C. using 0.25 g. polymer per 100 ml. of a solvent consisting of 60% phenol and 40% tetrachloroethane. The polyester fabrics, yarns, fibers and filaments that are dyed with the novel azo compounds can also contain minor amounts of other additives such as brighteners, pigments, delusterants, inhibitors, stabilizers, etc. Although the compounds of the invention are particularly suitable for dyeing polyester textile materials, the compounds can also be used to dye other synthetic, hydrophobic textile materials such as cellulose acetate, modified polypropylene, polyamide, modacrylic, etc. fibers.

The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove.

We claim:

1. A compound having the formula R is phenyl substituted at the ortho and/or para positions with not more than 3 substituents selected from the group consisting of lower alkyl, lower alkoxy, aryl, nitro, chlorine, bromine, formyl, lower alkanoyl, lower alkoxycarbonyl, aroyl, cyano, lower alkylsulfonyl, arylsulfonyl, trifluoromethyl, sulfamoyl, lower alkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, or thiocyanato, in which each aryl group is phenyl or phenyl substituted with lower alkyl, lower alkoxy, chlorine or bromine;

R is p-phenylene; p-phenylene substituted with lower alkyl, lower alkoxy, chlorine, bromine or the group --'NILA in which A is formyl, lower alkanoyl, lower cyanoalkanoyl, lower alkoxy lower alkanoyl, lower hydroxyalkanoyl, lower alkylsulfonyl-lower-alkanoyl, lower phenylalkanoyl, benzoyl, lower alkylbenzoyl, lower alkoxybenzoyl, chlorobenzoyl, bromobenzoyl, cyclohexylcarbonyl, lower alkoxycarbonyl, phenoxycarbonyl, lower alkylphenoxycarbonyl, lower alkoxyphenoxycarbonyl, chlorophenoxycarbonyl, bromophenoxycarbonyl, lower alkylsulfonyl, lower cyanoalkylsulfonyl, lower hydroxyalkylsulfonyl, lower chloroalkylsulfonyl, bromoalkylsulfonyl, phenylsulfonyl, lower alkylphenylsulfowherein R is hydrogen, chlorine, bromine, cyano or nitro; r R is nitro, lower alkylsulfonyl, thiocyanato, or sulfamoyl; nad R is hydrogen, chlorine, bromine, formyl, lower alkanoyl, lower alkoxycarbonyl, trifluoromethyl, lower alikylsulfonyl, cyano, sulfamoyl, or carbamoyl. 3. A compound according to claim 1 having the formula cH2 R5 N=N R is hydrogen, cyano, or nitro;

R is nitro, lower alkylsulfonyhor thicyanato;

R" is hydrogen, chlorine, bromine, formyl, lower alkanoyl, lower alkoxycarbonyl, trifluoromethyl, lower alkylsulfonyl, or cyano;

A is lower alkanoyl, benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl, or lower alkylcarbamoyl;

R is hydrogen, lower alkyl, lower alkoxy or chlorine;

bromine, and

R is lower alkyl.

4. A compound according to claim 1 having the formula c1 mrcocrr 'G 5. A compound according to claim 1 having the forwherein CH2@ 1 mucosa Q mula 6. A compound according to claim 1 having the formula 19 2O 71 A compound according to claim 1 having the for- References Cited UNITED STATES PATENTS me 2,117,733 5/1938 Krzikalla et a1 260-205 02H 5 2,249,749 7/1941 Dickey et a1. 260152 3,329,669 7/1967 1Sartori 260158 1 111100011 CHE-QGOOCHQ 3,478,011 11/1969 Artz 26o 20s 8. A compound according to claim 1 having the for- 3,483,180 12/1969 Ramanathan mula l0 FLOYD DALE HIGEL, Primary Examiner us. 01., X.R. N- 2 60-152, 158, 207.1, 471 R, 471 A H COOCH r ON 10 NHCOCHQ 

